Highly active supported catalyst compositions

ABSTRACT

This invention relates to metallocene catalyst compositions which are highly active for the polymerization of olefins, particularly prochiral α-olefins. The catalyst compositions contain at least one metallocene, and least one activator and a support that has been fluorided using a fluoride containing compound.

[0001] This is a Regular Application based on a Provisional ApplicationNo. 60/098007 filed on Aug. 26, 1998.

FIELD OF INVENTION

[0002] This invention relates generally to supported catalysts, and moreparticularly to supported metallocene catalysts and methods for theirproduction and use.

BACKGROUND

[0003] Metallocene catalyst systems and their use for olefinpolymerization are well known. Metallocene catalysts are single-sitedand differently activated compared to conventional Ziegler-Nattacatalysts. A typical metallocene catalyst system includes a metallocenecatalyst, a support, and an activator. Upon attaching or “fixing” thecatalyst to the support, the catalyst is generally referred to as asupported catalyst. For many polymerization processes, supportedcatalysts are required, and various methods for attaching metallocenecatalysts to a support are known in the art. Supports suitable for usewith metallocene catalyst are generally porous materials and can includeorganic materials, inorganic materials and inorganic oxides.

[0004] However, many supports contain reactive functionalities. In someinstances, these reactive functionalities may deactivate or reduce theactivity of the catalyst fixed to the support. When this occurs, theaddition of more catalyst to the catalyst system may be necessary toensure sufficient polymer production during olefin polymerization.Increasing the catalyst concentration in the catalyst system tocompensate for activity reduction caused by reactive functionalities isgenerally undesirable for many reasons. For instance, generally theaddition of more catalyst may also require the addition of moreactivator. As such, increasing the concentrations of both catalyst andactivator to overcome the effects of catalyst deactivation by reactivefunctionalities substantially increases the cost of olefinpolymerization.

[0005] Hydroxyl groups are an example of a reactive functionalitypresent on some supports which deactivate metallocene catalysts.Hydroxyl groups are present on supports, such as inorganic oxides. Anexample of an inorganic oxide is silica gel. As such, when using silicagel to support a metallocene catalyst, it is desirable to remove, reduceor render inactive a sufficient number of the hydroxyl groups. Methodsof removing or reducing hydroxyl groups include thermal and/or chemicaltreatments. The removal of hydroxyl groups is known as dehydroxylation.

[0006] Thermally treating or heating the support material generallyavoids contamination of the support by undesirable chemicals. However,in the case of many porous supports, such as silica gel, heating thesupport may fail to achieve sufficient dehydroxylation. Chemicallytreating the support material can be expensive and may result incontamination of the support.

[0007] Thus, there remains a need for increasing the activity ofsupported metallocene catalyst systems. Particularly, there remains aneed for improved supported metallocene catalysts wherein the reactivefunctionalities of the support are reduced and/or deactivated.

SUMMARY OF THE INVENTION

[0008] The present invention provides a highly active metallocenesupported catalyst composition. Generally, the inventor has discoveredthat when at least one metallocene catalyst is bound to a fluoridedsupport, the activity of this metallocene supported catalyst compositionis higher compared to the activity of the same metallocene catalystbound to a non-fluorided support. These non-fluorided supports includedsupports to which no fluorine was added or a halide other than fluorinewas added.

[0009] In one embodiment, the metallocene supported catalyst compositionincludes a metallocene catalyst and a support composition. The supportcomposition may be represented by the formula: Sup F, wherein Sup is asupport, and F is a fluorine atom bound to the support. The supportcomposition may be a fluorided support composition.

[0010] In another embodiment, the metallocene supported catalystcomposition includes a support composition represented by the formula:Sup L F_(n). “Sup” may further be defined as a support selected from thegroup which includes talc, clay, silica, alumina, magnesia, zirconia,iron oxides, boria, calcium oxide, zinc oxide, barium oxide, thoria,aluminum phosphate gel, polyvinylchloride and substituted polystyreneand mixtures thereof.

[0011] “L” is a first member selected from the group which includes (i)bonding, sufficient to bound the F to the Sup; (ii) B, Ta, Nb, Ge, Ga,Sn, Si, P, Ti, Mo, Re, or Zr bound to the Sup and to the F; and (iii) Obound to the Sup and bound to a second member selected from the groupconsisting of B, Ta, Nb, Ge, Ga, Sn, Si, P, Ti, Mo, Re, or Zr which isbound to the F;

[0012] “F” is a fluorine atom; and

[0013] “n” is a number from 1-7.

[0014] The support composition desirably may be a fluorided supportcomposition. The metallocene supported catalyst composition may alsoinclude boron and may also include an activator, such as alkylalumoxaneor MAO or haloaryl boron or aluminum compounds.

[0015] The metallocene catalyst may be represented by the formula:Cp_(m)MR_(n)X_(q), wherein Cp is a cyclopentadienyl ring which may besubstituted, or derivative thereof which may be substituted, M is aGroup 4, 5, or 6 transition metal, R is a hydrocarbyl group orhydrocarboxy group having from one to 20 carbon atoms, X may be ahalide, a hydride, an alkyl group, an alkenyl group or an arylalkylgroup, and m=1-3, n=0-3, q=0-3, and the sum of m+n+q is equal to theoxidation state of the transition metal.

[0016] The present invention also provides a method of making themetallocene supported catalyst composition. The method step includescontacting the metallocene catalyst with a support composition,desirably a fluorided support composition, under suitable conditions andfor a sufficient time, wherein the support composition is represented bythe formula Sup L F_(n). The support composition, and particularly thefluorided support composition, may be made by contacting a hydroxylgroup containing support material with at least one inorganic fluorideunder suitable conditions and for a sufficient time wherein the fluoridebecomes bound to the support.

[0017] The present invention also provides an olefin polymerizationmethod. The steps of the olefin polymerization method include contactinga polymerizable olefin with the metallocene supported catalystcomposition under suitable conditions and for a sufficient time.Desirably, the polymerizable material is propylene. The polymerizableolefin may be formed into numerous articles, such as, for example,films, fibers, fabrics, and molded structures.

DETAIL DESCRIPTION OF THE INVENTION

[0018] This invention is directed to metallocene catalyst compositionscomprising the reaction product of at least three components: (1) one ormore metallocenes; (2) one or more activators; and (3) one or morefluorided support compositions.

[0019] As used herein, the phrase “fluorided support composition” meansa support, desirably particulate and porous, which has been treated withat least one inorganic fluorine containing compound. For example, thefluorided support composition can be a silicon dioxide support wherein aportion of the silica hydroxyl groups has been replaced with fluorine orfluorine containing compounds.

[0020] As used herein, the term “support composition” means a support,desirably particulate and porous, which has been treated with at leastone fluorine containing compound. Suitable fluorine containing compoundsinclude, but are not limited to, inorganic fluorine containing compoundsand/or organic fluorine containing compounds.

[0021] In the specification, including the examples certainabbreviations may be used to facilitate the description. These mayinclude: Me=methyl, Et=ethyl, Bu=butyl, Ph=phenyl, Cp=cyclopentadienyl,Cp*=pentamethyl cyclopentadienyl, Ind=indenyl, Ti=titanium, Hf=hafnium,Zr=zirconium, O=oxygen, Si=silicon B=boron, Ta=tantalum, Nb=niobium,Ge=germanium, Mg=magnesium, Al=aluminum, Fe=iron, Th=thorium,Ga=gallium, P=phosphorus, Mo=molybdenum, Re=rhenium, and Sn=tin.

[0022] Supports

[0023] Supports suitable for use in this invention are generally porousmaterials and can include organic materials, inorganic materials andinorganic oxides. Desirably, supports suitable for use in this inventioninclude talc, clay, silica, alumina, magnesia, zirconia, iron oxides,boria, calcium oxide, zinc oxide, barium oxide, thoria, aluminumphosphate gel, polyvinylchloride and substituted polystyrene andmixtures thereof.

[0024] Particulate silicon dioxide materials are well known and arecommercially available from a number of commercial suppliers. Desirablythe silicon dioxide used herein is porous and has a surface area in therange of from about 10 to about 700 m²/g, a total pore volume in therange of from about 0.1 to about 4.0 cc/g and an average particlediameter in the range of from about 10 to about 500 μm. More desirably,the surface area is in the range of from about 50 to about 500 m²/g, thepore volume is in the range of from about 0.5 to about 3.5 cc/g and theaverage particle diameter is in the range of from about 15 to about 150μm. Most desirably the surface area is in the range of from about 100 toabout 400 m²/g, the pore volume is in the range of from about 0.8 toabout 3.0 cc/g and the average particle diameter is in the range of fromabout 20 to about 100 μm. The average pore diameter of typical poroussilicon dioxide support materials is in the range of from about 10 toabout 1000 Å. Desirably, the support material has an average porediameter of from about 50 to about 500 Å, and most desirably from about75 to about 350 Å.

[0025] Fluorine Compounds

[0026] The fluorine compounds suitable for providing fluorine for thesupport are desirably inorganic fluorine containing compounds. Suchinorganic fluorine containing compounds may be any compound containing afluorine atom as long as it does not contain a carbon atom. Particularlydesirable are inorganic fluorine containing compounds selected from thegroup consisting of NH₄BF₄, (NH₄)₂SiF₆, NH₄PF₆, NH₄F, (NH₄)₂TaF₇,NH₄NbF₄, (NH₄)₂GeF₆, (NH₄)₂SmF₆, (NH₄)₂TiF₆, (NH₄)₂ZrF₆, MoF₆, ReF₆,GaF₃, SO₂ClF, F₂, SiF₄, SF₆, ClF₃, ClF₅, BrF₅, IF₇, NF₃, HF, BF₃, NHF₂and NH₄HF₂. Of these, ammonium hexafluorosilicate and ammoniumtetrafluoroborate are more desirable.

[0027] Ammonium hexafluorosilicate and ammonium tetrafluoroboratefluorine compounds are typically solid particulates as are the silicondioxide supports. A desirable method of treating the support with thefluorine compound is to dry mix the two components by simply blending ata concentration of from 0.01 to 10.0 millimole F/g of support, desirablyin the range of from 0.05 to 6.0 millimole F/g of support, and mostdesirably in the range of from 0.1 to 3.0 millimole F/g of support. Thefluorine compound can be dry mixed with the support either before orafter charging to the vessel for dehydration or calcining the support.Accordingly, the fluorine concentration present on the support is in therange of from 0.6 to 3.5 wt % of support.

[0028] Another method of treating the support with the fluorine compoundis to dissolve the fluorine in a solvent, such as water, and thencontact the support with the fluorine containing solution. When water isused and silica is the support, it is desirable to use a quantity ofwater which is less than the total pore volume of the support.

[0029] Dehydration or calcining of the silica is not necessary prior toreaction with the fluorine compound. Desirably the reaction between thesilica and fluorine compound is carried out at a temperature of fromabout 100° C. to about 1000° C., and more desirably from about 200° C.to about 600° C. for about two to eight hours.

[0030] In one embodiment, the resulting support composition may begenerically represented by the formula:

Sup F

[0031] “Sup” is a support, “F” is a fluorine atom bound to the support.The fluorine atom may be bound, directly or indirectly, chemically orphysically to the support. An example of chemical or physical bondingwould be covalent and ionic bonding, respectively. The supportcomposition desirably may be a fluorided support composition.

[0032] In another embodiment, the resulting support composition, such asa fluorided support composition, may be generically represented by theformula:

Sup L F_(n)

[0033] “Sup” is a support selected from the group which includes talc,clay, silica, alumina, magnesia, zirconia, iron oxides, boria, calciumoxide, zinc oxide, barium oxide, thoria, aluminum phosphate gel,polyvinylchloride and substituted polystyrene.

[0034] “L” is a first member selected from the group which includes (i)bonding, sufficient to bound the F to the Sup; (ii) B, Ta, Nb, Ge, Ga,Sn, Si, P, Ti, Mo, Re, or Zr bound to the Sup and to the F; and (iii) 0bound to the Sup and bound to a second member selected from the groupconsisting of B, Ta, Nb, Ge, Ga, Sn, Si, P, Ti, Mo, Re, or Zr which isbound to the F;

[0035] “F” is a fluorine atom; and

[0036] “n” is a number from 1-7.

[0037] An example of such bonding sufficient to bound the F to the Supwould be chemical or physical bonding, such as, for example, covalentand ionic bonding. The support composition desirably may be a fluoridedsupport composition.

[0038] Metallocenes

[0039] As used herein the term “metallocene” means one or more compoundsrepresented by the formula Cp_(m)MR_(n)X_(q) wherein Cp is acyclopentadienyl ring which may be substituted, or derivative thereofwhich may be substituted, M is a Group 4, 5, or 6 transition metal, forexample titanium, zirconium, hafnium, vanadium, niobium, tantalum,chromium, molybdenum and tungsten, R is a hydrocarbyl group orhydrocarboxy group having from one to 20 carbon atoms, X may be ahalide, a hydride, an alkyl group, an alkenyl group or an arylalkylgroup, and m=1-3, n=0-3, q=0-3, and the sum of m+n+q is equal to theoxidation state of the transition metal.

[0040] Methods for making and using metallocenes are very well known inthe art. For example, metallocenes are detailed in U.S. Pat. Nos.4,530,914; 4,542,199; 4,769,910; 4,808,561; 4,871,705; 4,933,403;4,937,299; 5,017,714; 5,026,798; 5,057,475; 5,120,867; 5,132,381;5,155,180, 5,198,401, 5,278,119; 5,304,614; 5,324,800; 5,350,723;5,391,790; 5,436,305 and 5,510,502 each fully incorporated herein byreference.

[0041] Desirably, the metallocenes are one or more of those consistentwith the formula:

[0042] wherein M is a metal of Group 4, 5, or 6 of the Periodic Tabledesirably, zirconium, hafnium and titanium, most desirably zirconium;

[0043] R¹ and R² are identical or different, desirably identical, andare one of a hydrogen atom, a C₁-C₁₀ alkyl group, desirably a C₁-C₃alkyl group, a C₁-C₁₀ alkoxy group, desirably a C₁-C₃ alkoxy group, aC₆-C₁₀ aryl group, desirably a C₆-C₈ aryl group, a C₆-C₁₀ aryloxy group,desirably a C₆-C₈ aryloxy group, a C₂-C₁₀ alkenyl group, desirably aC₂-C₄ alkenyl group, a C₇-C₄₀ arylalkyl group, desirably a C₇-C₁₀arylalkyl group, a C₇-C₄₀ alkylaryl group, desirably a C₇-C₁₂ alkylarylgroup, a C₈-C₄₀ arylalkenyl group, desirably a C₈-C₁₂ arylalkenyl group,or a halogen atom, desirably chlorine;

[0044] R⁵ and R⁶ are identical or different, desirably identical, areone of a halogen atom, desirably a fluorine, chlorine or bromine atom, aC₁-C₁₀ alkyl group, desirably a C₁-C₄ alkyl group, which may behalogenated, a C₆-C₁₀ aryl group, which may be halogenated, desirably aC₆-C₈ aryl group, a C₂-C₁₀ alkenyl group, desirably a C₂-C₄ alkenylgroup, a C₇-C₄₀-arylalkyl group, desirably a C₇-C₁₀ arylalkyl group, aC₇-C₄₀ alkylaryl group, desirably a C₇-C₁₂ alkylaryl group, a C₈-C₄₀arylalkenyl group, desirably a C₈-C₁₂ arylalkenyl group, a —NR₂ ¹⁵,—SR¹⁵, —OR¹⁵, —OSiR₃ ¹⁵ or —PR₂ ¹⁵ radical, wherein R¹⁵ is one of ahalogen atom, desirably a chlorine atom, a C₁-C₁₀ alkyl group, desirablya C₁-C₃ alkyl group, or a C₆-C₁₀ aryl group, desirably a C₆-C₉ arylgroup;

[0045] wherein:

[0046] R¹¹, R¹² and R¹³ are identical or different and are a hydrogenatom, a halogen atom, a C₁-C₂₀ alkyl group, desirably a C₁-C₁₀ alkylgroup, a C₁-C₂₀ fluoroalkyl group, desirably a C₁-C₁₀ fluoroalkyl group,a C₆-C₃₀ aryl group, desirably a C₆-C₂₀ aryl group, a C₆-C₃₀ fluoroarylgroup, desirably a C₆-C₂₀ fluoroaryl group, a C₁-C₂₀ alkoxy group,desirably a C₁-C₁₀ alkoxy group, a C₂-C₂₀ alkenyl group, desirably aC₂-C₁₀ alkenyl group, a C₇-C₄₀ arylalkyl group, desirably a C₇-C₂₀arylalkyl group, a C₈-C₄₀ arylalkenyl group, desirably a C₈-C₂₂arylalkenyl group, a C₇-C₄₀ alkylaryl group, desirably a C₇-C₂₀alkylaryl group or R¹¹ and R¹², or R¹¹ and R¹³, together with the atomsbinding them, can form ring systems;

[0047] M² is silicon, germanium or tin, desirably silicon or germanium,most desirably silicon;

[0048] R⁸ and R⁹ are identical or different and have the meanings statedfor R¹¹;

[0049] m and n are identical or different and are zero, 1 or 2,desirably zero or 1, m plus n being zero, 1 or 2, desirably zero or 1;and

[0050] the radicals R³, R⁴, and R¹⁰ are identical or different and havethe meanings stated for R¹¹, R¹² and R¹³. Two adjacent R¹⁰ radicals canbe joined together to form a ring system, desirably a ring systemcontaining from about 4-6 carbon atoms.

[0051] Alkyl refers to straight or branched chain substituents. Halogen(halogenated) refers to fluorine, chlorine, bromine or iodine atoms,desirably fluorine or chlorine.

[0052] Particularly desirable transition metal compounds are compoundsof the structures (A) and (B):

[0053] wherein:

[0054] M¹ is Zr or Hf, R¹ and R² are methyl or chlorine, and R⁵, R⁶ R⁸,R⁹,R¹⁰, R¹¹ and R¹² have the above-mentioned meanings.

[0055] Illustrative but non-limiting examples of desirable transitionmetal compounds include:

[0056] Dimethylsilandiylbis(2-methyl-4-phenyl-1-indenyl)Zirconiumdimethyl

[0057] Dimethylsilandiylbis(2-methyl-4,5-benzoindenyl) Zirconiumdimethyl;

[0058] Dimethylsilandiylbis(2-methyl-4,6-diisopropylindenyl) Zirconiumdimethyl;

[0059] Dimethylsilandiylbis(2-ethyl-4-phenyl-1-indenyl) Zirconiumdimethyl;

[0060] Dimethylsilandiylbis (2-ethyl-4-naphthyl-1-indenyl) Zirconiumdimethyl,

[0061] Phenyl(methyl)silandiylbis(2-methyl-4-phenyl-1-indenyl) Zirconiumdimethyl,

[0062] Dimethylsilandiylbis(2-methyl-4-(1-naphthyl)-1-indenyl) Zirconiumdimethyl,

[0063] Dimethylsilandiylbis(2-methyl-4-(2-naphthyl)-1-indenyl) Zirconiumdimethyl,

[0064] Dimethylsilandiylbis(2-methyl-indenyl) Zirconium dimethyl,

[0065] Dimethylsilandiylbis(2-methyl-4,5-diisopropyl-1-indenyl)Zirconium dimethyl,

[0066] Dimethylsilandiylbis(2,4,6-trimethyl-1-indenyl) Zirconiumdimethyl,

[0067]Phenyl(methyl)silandiylbis(2-methyl-4,6-diisopropyl-1-indenyl)Zirconiumdimethyl,

[0068] 1,2-Ethandiylbis(2-methyl-4,6-diisopropyl-1-indenyl) Zirconiumdimethyl,

[0069] 1,2-Butandiylbis(2-methyl-4,6-diisopropyl-1-indenyl) Zirconiumdimethyl,

[0070] Dimethylsilandiylbis(2-methyl-4-ethyl-1-indenyl) Zirconiumdimethyl,

[0071] Dimethylsilandiylbis(2-methyl-4-isopropyl-1-indenyl) Zirconiumdimethyl,

[0072] Dimethylsilandiylbis(2-methyl-4-t-butyl-1-indenyl) Zirconiumdimethyl,

[0073] Phenyl(methyl)silandiylbis(2-methyl-4-isopropyl-1-indenyl)Zirconium dimethyl,

[0074] Dimethylsilandiylbis(2-ethyl-4-methyl-1-indenyl) Zirconiumdimethyl,

[0075] Dimethylsilandiylbis(2,4-dimethyl-1-indenyl) Zirconium dimethyl,

[0076] Dimethylsilandiylbis(2-methyl-4-ethyl-1-indenyl) Zirconiumdimethyl,

[0077] Dimethylsilandiylbis(2-methyl-α-acenaphth-1-indenyl) Zirconiumdimethyl,

[0078] Phenyl(methyl)silandiylbis (2-methyl-4,5-benzo-1-indenyl)Zirconium dimethyl,

[0079]Phenyl(methyl)silandiylbis(2-methyl-4,5-(methylbenzo)-1-indenyl)Zirconiumdimethyl,

[0080]Phenyl(methyl)silandiylbis(2-methyl-4,5-(tetramethylbenzo)-1-indenyl)Zirconiumdimethyl,

[0081]Phenyl(methyl)silandiylbis(2-methyl-a-acenaphth-1-indenyl)Zirconiumdimethyl,

[0082] 1,2-Ethandiylbis(2-methyl-4,5-benzo-1-indenyl) Zirconiumdimethyl,

[0083] 1,2-Butandiylbis(2-methyl-4,5-benzo-1-indenyl) Zirconiumdimethyl,

[0084] Dimethylsilandiylbis(2-methyl-4,5-benzo-1-indenyl) Zirconiumdimethyl,

[0085] 1,2-Ethandiylbis(2,4,7-trimethyl-1-indenyl) Zirconium dimethyl,

[0086] Dimethylsilandiylbis(2-methyl-1-indenyl) Zirconium dimethyl,

[0087] 1,2-Ethandiylbis(2-methyl-1-indenyl) Zirconium dimethyl,

[0088] Phenyl(methyl)silandiylbis(2-methyl-1-indenyl) Zirconiumdimethyl,

[0089] Diphenylsilandiylbis(2-methyl-1-indenyl) Zirconium dimethyl,

[0090] 1,2-Butandiylbis(2-methyl-1-indenyl) Zirconium dimethyl,

[0091] Dimethylsilandiylbis(2-ethyl-1-indenyl) Zirconium dimethyl,

[0092] Dimethylsilandiylbis(2-methyl-5-isobutyl-1-indenyl) Zirconiumdimethyl,

[0093] Phenyl(methyl)silandiylbis(2-methyl-5-isobutyl-1-indenyl)Zirconium dimethyl,

[0094] Dimethylsilandiylbis(2-methyl-5-t-butyl-1-indenyl) Zirconiumdimethyl,

[0095] Dimethylsilandiylbis(2,5,6-trimethyl-1-indenyl) Zirconiumdimethyl,

[0096] Dimethylsilandiylbis (2-methyl-4-phenyl-1-indenyl)Zirconiumdichloride

[0097] Dimethylsilandiylbis(2-methyl-4,5-benzoindenyl) Zirconiumdichloride,

[0098] Dimethylsilandiylbis(2-methyl-4,6-diisopropylindenyl) Zirconiumdichloride,

[0099] Dimethylsilandiylbis(2-ethyl-4-phenyl-1-indenyl) Zirconiumdichloride,

[0100] Dimethylsilandiylbis (2-ethyl-4-naphthyl-1-indenyl) Zirconiumdichloride,

[0101] Phenyl(methyl)silandiylbis(2-methyl-4-phenyl-1-indenyl) Zirconiumdichloride,

[0102] Dimethylsilandiylbis(2-methyl-4-(1-naphthyl)-1-indenyl) Zirconiumdichloride,

[0103] Dimethylsilandiylbis(2-methyl-4-(2-naphthyl)-1-indenyl) Zirconiumdichloride,

[0104] Dimethylsilandiylbis(2-methyl-indenyl) Zirconium dichloride,

[0105] Dimethylsilandiylbis(2-methyl-4,5-diisopropyl-1-indenyl)Zirconium dichloride,

[0106] Dimethylsilandiylbis(2,4,6-trimethyl-1-indenyl) Zirconiumdichloride,

[0107] Phenyl(methyl)silandiylbis(2-methyl-4,6-diisopropyl-1-indenyl)Zirconium dichloride,

[0108] 1,2-Ethandiylbis(2-methyl-4,6-diisopropyl-1-indenyl) Zirconiumdichloride,

[0109] 1,2-Butandiylbis(2-methyl-4,6-diisopropyl-1-indenyl) Zirconiumdichloride,

[0110] Dimethylsilandiylbis(2-methyl-4-ethyl-1-indenyl) Zirconiumdichloride,

[0111] Dimethylsilandiylbis(2-methyl-4-isopropyl-1-indenyl) Zirconiumdichloride,

[0112] Dimethylsilandiylbis(2-methyl-4-t-butyl-1-indenyl) Zirconiumdichloride,

[0113] Phenyl(methyl)silandiylbis(2-methyl-4-isopropyl-1-indenyl)Zirconium dichloride,

[0114] Dimethylsilandiylbis(2-ethyl-4-methyl-1-indenyl) Zirconiumdichloride,

[0115] Dimethylsilandiylbis(2,4-dimethyl-1-indenyl) Zirconiumdichloride,

[0116] Dimethylsilandiylbis(2-methyl-4-ethyl-1-indenyl) Zirconiumdichloride,

[0117] Dimethylsilandiylbis(2-methyl-α-acenaphth-1-indenyl) Zirconiumdichloride,

[0118] Phenyl(methyl)silandiylbis(2-methyl-4,5-benzo-1-indenyl)Zirconium dichloride,

[0119] Phenyl(methyl)silandiylbis(2-methyl-4,5-(methylbenzo)-1-indenyl)Zirconium dichloride,

[0120]Phenyl(methyl)silandiylbis(2-methyl-4,5-(tetramethylbenzo)-1-indenyl)Zirconium dichloride,

[0121] Phenyl(methyl)silandiylbis (2-methyl-a-acenaphth-1-indenyl)Zirconium dichloride,

[0122] 1,2-Ethandiylbis(2-methyl-4,5-benzo-1-indenyl) Zirconiumdichloride,

[0123] 1,2-Butandiylbis(2-methyl-4,5-benzo-1-indenyl) Zirconiumdichloride,

[0124] Dimethylsilandiylbis(2-methyl-4,5-benzo-1-indenyl) Zirconiumdichloride,

[0125] 1,2-Ethandiylbis(2,4,7-trimethyl-1-indenyl) Zirconium dichloride,

[0126] Dimethylsilandiylbis(2-methyl-1-indenyl) Zirconium dichloride,

[0127] 1,2-thandiylbis(2-methyl-1-indenyl) Zirconium dichloride,

[0128] Phenyl(methyl)silandiylbis(2-methyl-1-indenyl) Zirconiumdichloride,

[0129] Diphenylsilandiylbis(2-methyl-1-indenyl) Zirconium dichloride,

[0130] 1,2-Butandiylbis(2-methyl-1-indenyl) Zirconium dichloride,

[0131] Dimethylsilandiylbis(2-ethyl-1-indenyl) Zirconium dichloride,

[0132] Dimethylsilandiylbis(2-methyl-5-isobutyl-1-indenyl) Zirconiumdichloride,

[0133] Phenyl(methyl)silandiylbis(2-methyl-5-isobutyl-1-indenyl)Zirconium dichloride,

[0134] Dimethylsilandiylbis(2-methyl-5-t-butyl-1-indenyl) Zirconiumdichloride,

[0135] Dimethylsilandiylbis(2,5,6-rimethyl -1-indenyl) Zirconiumdichloride, and the like.

[0136] Many of these desirable transition metal compound components aredescribed in detail in U.S. Pat. Nos. 5,145,819; 5,243,001; 5,239,022;5,329,033; 5,296,434; 5,276,208; 5,672,668, 5,304,614 and 5,374,752; andEP 549 900 and 576 970 all of which are herein fully incorporated byreference.

[0137] Additionally, metallocenes such as those described in U.S. Pat.Nos. 5,510,502, 4,931,417, 5,532,396, 5,543,373, WO 98/014585, EP611 773and WO 98/22486 (each fully incorporated herein by reference) aresuitable for use in this invention.

[0138] Activators

[0139] Metallocenes are generally used in combination with some form ofactivator in order to create an active catalyst system. The term“activator” is defined herein to be any compound or component, orcombination of compounds or components, capable of enhancing the abilityof one or more metallocenes to polymerize olefins to polyolefins.Alklyalumoxanes such as methylalumoxane (MAO) are commonly used asmetallocene activators. Generally alkylalumoxanes contain about 5 to 40of the repeating units:

[0140] AIR₂ for linear species and

[0141] for cyclic species

[0142] where R is a C₁-C₈ alkyl including mixed alkyls. Particularlydesirable are the compounds in which R is methyl. Alumoxane solutions,particularly methylalumoxane solutions, may be obtained from commercialvendors as solutions having various concentrations. There are a varietyof methods for preparing alumoxane, non-limiting examples of which aredescribed in U.S. Pat. Nos. 4,665,208, 4,952,540, 5,091,352, 5,206,199,5,204,419, 4,874,734, 4,924,018, 4,908,463, 4,968,827, 5,308,815,5,329,032, 5,248,801, 5,235,081, 5,103,031 and EP-A-0 561 476, EP-B1-0279 586, EP-A-0 594-218 and WO 94/10180, each fully incorporated hereinby reference. (as used herein unless otherwise stated “solution” refersto any mixture including suspensions.)

[0143] Ionizing activators may also be used to activate metallocenes.These activators are neutral or ionic, or are compounds such astri(n-butyl)ammonium tetrakis(pentaflurophenyl)borate, which ionize theneutral metallocene compound. Such ionizing compounds may contain anactive proton, or some other cation associated with, but not coordinatedor only loosely coordinated to, the remaining ion of the ionizingcompound. Combinations of activators may also be used, for example,alumoxane and ionizing activators in combinations, see for example, WO94/07928.

[0144] Descriptions of ionic catalysts for coordination polymerizationcomprised of metallocene cations activated by non-coordinating anionsappear in the early work in EP-A-0 277 003, EP-A-0 277 004 and U.S. Pat.No. 5,198,401 and WO-A-92/00333 (incorporated herein by reference).These teach a desirable method of preparation wherein metallocenes(bisCp and monoCp) are protonated by an anion precursor such that analkyl/hydride group is abstracted from a transition metal to make itboth cationic and charge-balanced by the non-coordinating anion.Suitable ionic salts include tetrakis-substituted borate or aluminumsalts having fluorided aryl-constituents such as phenyl, biphenyl andnapthyl.

[0145] The term “noncoordinating anion” (NCA) means an anion whicheither does not coordinate to said cation or which is only weaklycoordinated to said cation thereby remaining sufficiently labile to bedisplaced by a neutral Lewis base. “Compatible” noncoordinating anionsare those which are not degraded to neutrality when the initially formedcomplex decomposes. Further, the anion will not transfer an anionicsubstituent or fragment to the cation so as to cause it to form aneutral four coordinate metallocene compound and a neutral by-productfrom the anion . Noncoordinating anions useful in accordance with thisinvention are those which are compatible, stabilize the metallocenecation in the sense of balancing its ionic charge in a +1 state, yetretain sufficient lability to permit displacement by an ethylenically oracetylenically unsaturated monomer during polymerization.

[0146] The use of ionizing ionic compounds not containing an activeproton but capable of producing both the active metallocene cation and anoncoordinating anion is also known. See, for example, EP-A-0 426 637and EP-A-0 573 403 (incorporated herein by reference). An additionalmethod of making the ionic catalysts uses ionizing anion precursorswhich are initially neutral Lewis acids but form the cation and anionupon ionizing reaction with the metallocene compounds, for example theuse of tris(pentafluorophenyl) borane. See EP-A-0 520 732 (incorporatedherein by reference). Ionic catalysts for addition polymerization canalso be prepared by oxidation of the metal centers of transition metalcompounds by anion precursors containing metallic oxidizing groups alongwith the anion groups, see EP-A-0 495 375 (incorporated herein byreference).

[0147] Where the metal ligands include halogen moieties (for example,bis-cyclopentadienyl zirconium dichloride) which are not capable ofionizing abstraction under standard conditions, they can be convertedvia known alkylation reactions with organometallic compounds such aslithium or aluminum hydrides or alkyls, alkylalumoxanes, Grignardreagents, etc. See EP-A-0 500 944 and EP-A1-0 570 982 (incorporatedherein by reference) for in situ processes describing the reaction ofalkyl aluminum compounds with dihalo-substituted metallocene compoundsprior to or with the addition of activating anionic compounds.

[0148] Desirable methods for supporting ionic catalysts comprisingmetallocene cations and NCA are described in U.S. Pat. No. 5,643,847,U.S. patent application Ser. No. 09184358, filed Nov. 2, 1998 and U.S.patent application Ser. No. 09184389, filed Nov. 2, 1998 (all fullyincorporated herein by reference). When using the support composition,and particularly the fluorided support composition, of this invention,these NCA support methods generally comprise using neutral anionprecursors that are sufficiently strong Lewis acids to react with thehydroxyl reactive functionalities present on the silica surface suchthat the Lewis acid becomes covalently bound.

[0149] In one embodiment of this invention, the activator is one or moreNCAs and the supportation method described above is used. This reactioncan be generically represented by the chemical formula:

[L_(n)L′_(m)M′R′]⁺[LA-O-SupLF_(n)]⁻(1)

[0150] where [L_(n)L′_(m)M′R′]⁺ is the catalytically active transitionmetal cation and LA-O- is the activator anion bound to the supportcomposition, particularly the fluorided support composition, SupLF_(n).More specifically, L_(n) is one or more ligands (n equals d⁰−1 where d⁰is the highest oxidation state of M′) covalently bound to M′, L′_(m) isa neutral, non-oxidizing ligand having a dative bond to M′ (typically mequals 0 to 3), M′ is a Group 4, 5, 6, 9, or 10 transition metal, R′ isa ligand having a δ bond to M′ into which a polymerizable monomer ormacromonomer can insert for coordination polymerization. LA is a Lewisacid that is capable of forming the anionic activator and O is oxygen.

[0151] The activator anion neutral precursors that serve as the Lewisacid (LA) include any of the noncoordinating anion precursors ofsufficient acidity to accept the available electron pair of the hydroxylgroup oxygen atom and facilitate the protonation of the transition metalcompound or a secondary proton acceptor (see below) by the silanol groupproton. The desirable activator anion neutral precursors that serve asthe Lewis acid (LA) are strong Lewis acids with non-hydrolyzableligands, at least one of which is electron-withdrawing, such as thoseLewis acids known to abstract an anionic fragment from dimethylzirconocene (biscyclopentadienyl zirconium dimethyl) e.g.,tris-perfluorophenyl borane, trisperfluoronaphthyl borane,trisperfluorobiphenyl borane. These precursors therefore should notpossess any reactive ligands, which can be protonated by any remaininghydroxyl groups on the support composition, particularly the fluoridedsupport composition. For example, any Group 13 element based Lewis acidshaving only alkyl, halo, alkoxy, and/or amido ligands, which are readilyhydrolyzed in aqueous media, may not be suitable. At least one ligand ofLA must be sufficiently electron-withdrawing to achieve the neededacidity, for example, tris-perfluorophenyl borane, under typicalreaction conditions. Typical metal/metalloid centers for LA will includeboron, aluminum, antimony, arsenic, phosphorous and gallium. Mostdesirably LA is a neutral compound comprising a Group 13 metalloidcenter with a complement of ligands together sufficientlyelectron-withdrawing such that the Lewis acidity is greater than orequal to that of AlCl₃. Examples include tris-perfluorophenylborane,tris(3,5-di(trifluoromethyl)phenyl)borane,tris(di-t-butylmethylsilyl)perfluorophenylborane, and other highlyfluorinated tris-arylborane compounds.

[0152] Additionally, when the activator for the metallocene supportedcatalyst composition is a NCA, desirably the NCA is first added to thesupport composition followed by the addition of the metallocenecatalyst. When the activator is MAO, desirably the MAO and metallocenecatalyst are dissolved together in solution. The support is thencontacted with the MAO/metallocene catalyst solution. Other methods andorder of addition will be apparent to those skilled in the art.

[0153] Polymerization

[0154] The metallocene supported catalyst composition is useful incoordination polymerization of unsaturated monomers conventionally knownto be polymerizable under coordination polymerization conditions. Suchconditions also are well known and include solution polymerization,slurry polymerization, and low pressure gas phase polymerization. Themetallocene supported catalysts compositions of the present inventionare thus particularly useful in the known operating modes employingfixed-bed, moving-bed, fluid-bed, or slurry processes conducted insingle, series or parallel reactors.

[0155] The metallocene supported catalyst composition of this inventionare particularly suitable for propylene polymerizations. Any process maybe used, but propylene polymerizations are most commonly conducted usinga slurry processes in which the polymerization medium can be either aliquid monomer, like propylene, or a hydrocarbon solvent or diluent,advantageously aliphatic paraffin such as propane, isobutane, hexane,heptane, cyclohexane, etc. or an aromatic diluent such as toluene. Thepolymerization temperatures may be those considered low, e.g., less than50° C., desirably 0° C. -30° C., or may be in a higher range, such as upto about 150° C., desirably from 50° C. up to about 80° C., or at anyranges between the end points indicated. Pressures can vary from about100 to about 700 psia (0.69-4.8 MPa). Additional description is given inU.S. Pat. Nos. 5,274,056 and 4,182,810 and WO 94/21962 which are eachfully incorporated by reference.

[0156] Propylene homopolymers may be formed with the metallocenesupported catalyst composition using conventional polymerizationtechniques. The microstructure of the homopolymer will desirably possessa meso run length as measured by ¹³C NMR of 70% or greater relative tothe total polymer produced. Copolymers with ethylene may be formed byintroduction of ethylene to the propylene slurry or gas phasepolymerization of gaseous propylene and ethylene comonomers. Copolymerswith ethylene desirably contain 0.1 to 10 wt % comonomer. Stereoregularhomopolymers and copolymers of α-olefins may be formed with this systemby introduction of the appropriate monomer or monomers to a slurry orbulk propylene process.

[0157] Pre-polymerization may also be used for further control ofpolymer particle morphology in typical slurry or gas phase reactionprocesses in accordance with conventional teachings. For example suchcan be accomplished by pre-polymerizing a C₂-C₆ alpha-olefin for alimited time, for example, ethylene is contacted with the supportedmetallocene catalyst composition at a temperature of −15 to 30° C. andethylene pressure of up to about 250 psig (1724 kPa) for 75 min. toobtain a polymeric coating on the support of polyethylene of30,000-150,000 molecular weight. The pre-polymerized catalyst is thenavailable for use in the polymerization processes referred to above. Ina similar manner, the activated catalyst on a support coated with apreviously polymerized thermoplastic polymer can be utilized in thesepolymerization processes.

[0158] Additionally it is desirable to reduce or eliminatepolymerization poisons that may be introduced via feedstreams, solventsor diluents, by removing or neutralizing the poisons. For example,monomer feed streams or the reaction diluent may be pre-treated, ortreated in situ during the polymerization reaction, with a suitablescavenging agent. Typically such will be an organometallic compoundemployed in processes such as those using the Group-13 organometalliccompounds of U.S. Pat. No. 5,153,157 and WO-A-91/09882 andWO-A-94/03506, noted above, and that of WO-A-93/14132.

EXAMPLES

[0159] The following examples are presented to illustrate the foregoingdiscussion. All parts, proportions and percentages are by weight unlessotherwise indicated. Although the examples may be directed to certainembodiments of the present invention, they are not to be viewed aslimiting the invention in any specific respect

[0160] Preparation of the Supports

[0161] The following example shows that silica can be fluorided duringthe silica gel heat dehydration process.

Example 1

[0162] 48.5 grams of SiO₂, available from Grace Davison, a subsidiary ofW. R. Grace Co.-Conn. as Sylopol®952 (“952 silica gel”) having N₂ porevolume 1.63 cc/g and a surface area of 312m²/g, was dry mixed with 1.5grams ammonium hexafluorosilicate available from Aldrich ChemicalCompany, Milwaukee Wis. The ammonium hexafluorosilicate addedcorresponds to 1.05 millimole F per gram silica gel. The mixture wastransferred to a 5 cm ID by 50 cm vycor glass tube having a medium fritplug 3.8 cm from one end. The tube was inserted into a tube furnace anda flow of N₂ (220 cc/min) was passed up through the frit to fluidize thesilica bed. The furnace was heated according to the following schedule.

[0163] Raise the temperature from 25 to 150° C. over 5 hours

[0164] Hold the temperature at 150° C. for 4 hours

[0165] Raise the temperature from 150 to 500° C. over 2 hours

[0166] Hold the temperature at 500° C. for 4 hours

[0167] Heat off and allow to cool under N₂

[0168] When cool the fluorided silica was stored under N₂. NeutronActivation Analysis, Nuclear Analytical Services, The University ofTexas at Austin, showed 1.68±0.06 weight percent (wt %) fluorine.

[0169] The following examples show that the weight percent fluoride onthe silica can be controlled by the amount and type of fluoridecontaining compound, such as an inorganic fluoride containing compound,added to the silica gel prior to the heat dehydration.

Examples 2 through 14

[0170] In a similar manner the 952 silica gel was treated as describedin Example 1 except different weights and fluorine compounds were used.Details are shown in Table 1. Column three describes the wt % offluorine compound present in the total silica/fluorine compound samplebefore heating. Column four labeled “added” describes the wt % offluorine present in the sample before heating. Column five labeled“found” describes the wt % of fluorine present in the sample afterheating. The wt % in column five is higher than column four reflecting,to some degree, the loss of water during heating. TABLE 1 500° C.Fluorided Silica Examples wt % of Fluorine Fluorine Fluorine (wt %)Example Compound Compound added Found 2 (NH₄)₂SiF₆ 0.5 0.32 0.77 ± 0.053 ″ 1 0.64 1.32 ± 0.05 4 ″ 2 1.28 1.68 ± 0.06 5 ″ 3 1.92 2.55 ± 0.09 6 ″4 2.56 3.04 ± 0.09 7 ″ 6 3.84 3.20 ± 0.10 8 NH₄BF₄ 1.8 1.28 n.d.¹ 9 ″3.6 2.56 1.89 ± 0.11 10 ″ ″ ″ 1.95 ± 0.06 11 (NH₄)₂PF₆ 1.8 1.28 1.66 ±0.06 12 ″ 3.6 2.56 2.20 ± 0.09 13 ″ ″ ″ 2.26 ± 0.06 14 NH₄F 2.5 1.281.68 ± 0.07

[0171] Examples 15-21 show that the silica gel can be fluorided duringheat dehydration at different temperatures.

Example 15

[0172] In a similar manner to Example 1, 48.15 grams of the 952 silicagel was dry mixed with 1.85 grams ammonium fluoride from AldrichChemical Company, Milwaukee Wis. The ammonium fluoride added correspondsto 1.05 millimole F per gram silica gel. The following heat schedule wasused.

[0173] Raise the temperature from 25 to 150° C. over 5 hours

[0174] Hold the temperature at 150° C. for 4 hours

[0175] Raise the temperature from 150 to 600° C. over 2 hours

[0176] Hold the temperature at 600° C. for 4 hours

[0177] Heat off and allow to cool under N₂

[0178] When cool the fluorided silica was stored under N₂. NeutronActivation Analysis showed 2.00±0.09 wt % fluorine.

Example 16

[0179] The 952 silica gel was treated as in Example 1 except thefollowing heat schedule was used.

[0180] Raise the temperature from 25 to 150° C. over 5 hours

[0181] Hold the temperature at 150° C. for 4 hours

[0182] Raise the temperature from 150 to 300° C. over 2 hours

[0183] Hold the temperature at 300° C. for 4 hours

[0184] Heat off and allow to cool under N₂

[0185] When cool the fluorided silica was stored under N₂.

Examples 17 through 21

[0186] In a similar manner the 952 silica gel was fluorided as inExample 16 except that different weights and fluorine Compounds wereused. Details are shown in Table 2. Similar to Table 1, column threedescribes the wt % of fluorine compound present in the totalsilica/fluorine compound sample before heating. Column four labeled“added” describes the wt % of fluorine present in the sample beforeheating. Column five labeled “found” describes the wt % of fluorinepresent in the sample after heating. The wt % in column five is higherthan column four reflecting, to some degree, the loss of water duringheating. TABLE 2 300° C. Fluorided Silica Examples wt % of FluorineFluorine Fluorine (wt %) Example Compound Compound Added Found 17(NH₄)₂SiF₆ 1 0.64 0.93 ± 0.05 18 ″ 2 1.28 1.55 ± 0.05 19 ″ 4 2.56 3.22 ±0.09 20 ″ 6 3.84 n.d.¹ 21 NH₄BF₄ 1.8 1.28 1.81 ± 0.06

[0187] Examples 22 and 23 show silica gels from other manufacturers canbe fluorided during heat dehydration.

Example 22

[0188] 48.5 grams of SiO₂, available from The PQ Corporation, ValleyForge Pa. as MS1340 having a surface area of 450 m²/g and pore volume of1.3 cc/g, was dry mixed with 1.5 grams ammonium hexafluorosilicateavailable from Aldrich Chemical Co. The mixture was transferred to thefluidized dehydrator described in Example 1 and a flow of N₂ (400cc/min) was passed through the unit. The furnace was heated according tothe following schedule.

[0189] Raise the temperature from 25 to 150° C. over 5 hours

[0190] Hold the temperature at 150° C. for 4 hours

[0191] Raise the temperature from 150 to 500° C. over 2 hours

[0192] Hold the temperature at 500° C. for 4 hours

[0193] Heat off and allow to cool under N₂

[0194] When cool the fluorided silica was stored under N₂. NeutronActivation Analysis showed 1.93±0.045 percent fluorine.

Example 23

[0195] 48.5 grams of SiO₂, available from Crosfield Limited, WarringtonEngland as MD682CM having a surface area of 280 m2/g and a pore volumeof 1.4 cc/g, was dry mixed with 1.5 grams ammonium hexafluorosilicateavailable from Aldrich Chemical Co. The mixture was transferred to thefluidized dehydrator described in Example 1 and a flow of N₂ (200cc/min) was passed through the unit. The furnace was heated according tothe following schedule.

[0196] Raise the temperature from 25 to 150° C. over 5 hours

[0197] Hold the temperature at 150° C. for 4 hours

[0198] Raise the temperature from 150 to 500° C. over 2 hours

[0199] Hold the temperature at 500° C. for 4 hours

[0200] Heat off and allow to cool under N₂

[0201] When cool the fluorided silica was stored under N₂. NeutronActivation Analysis showed 1.96±0.052 percent fluorine.

[0202] Comparative Examples 1-10 describe the preparation ofnon-fluorided, dehydrated silicas for comparison as supports to thefluorided silicas.

Comparative Example 1

[0203] 50.0 grams of SiO₂(952 silica gel), was transferred to a 5 cm IDby 50 cm vycor glass tube having a medium frit plug 3.8 cm from one end.The tube was inserted into a tube furnace and a flow of N₂ (220 cc/min)was passed through the frit to fluidize the silica bed. The furnace washeated according to the following schedule.

[0204] Raise the temperature from 25 to 150° C. over 5 hours

[0205] Hold the temperature at 150° C. for 4 hours

[0206] Raise the temperature from 150 to 800° C. over 2 hours

[0207] Hold the temperature at 800° C. for 4 hours

[0208] Heat off and allow to cool under N₂

[0209] When cool the dehydrated silica was stored under N₂.

Comparative Example 2

[0210] In a similar manner the 952 silica gel was dehydrated with thesame schedule as Comparative Example 1 except the maximum temperaturewas 600° C. When cool the dehydrated silica was stored under N₂.

Comparative Example 3

[0211] In a similar manner the 952 silica gel was dehydrated with thesame schedule as Comparative Example 1 except the maximum temperaturewas 500° C. When cool the dehydrated silica was stored under N₂.

Comparative Example 4

[0212] In a similar manner Sylopol®948 silica gel (“948 silica gel”)having a pore volume of 1.7 cc/g and a surface area of 335 m2/g,available from Grace Davison, a subsidiary of W. R. Grace Co.-Conn. wasdehydrated with the same schedule as Comparative Example 3. When coolthe dehydrated silica was stored under N₂.

Comparative Example 5

[0213] In a similar manner the 952 silica gel was dehydrated with thesame schedule as Comparative Example 1 except the maximum temperaturewas 300° C. When cool the dehydrated silica was stored under N₂.

[0214] The Comparative Example 6 describes the preparation of anon-fluorided, chemically dehydrated silica for comparison as a supportto fluorided silica.

Comparative Example 6

[0215] 25.00 g of the silica prepared in Comparative Example 4 wasloaded to a 1000 milliliter flask and 250 ml hexane added. To the slurryunder stirring was added 5.3 milliliters hexamethyldisilazane, availablefrom Aldrich Chemical Company, Milwaukee Wis. After the dropwiseaddition was complete the slurry was stirred for 30 minutes thenrefluxed for 120 minutes. When cool the flask was taken into the drybox. The supernatant was decanted then the slurry washed two times withhexane, two times with isopentane and dried under vacuum at ambienttemperature. Obtained 25.76 grams of chemically dehydrated silica. Thedehydrated silica was stored under N₂.

[0216] The Comparative Example 7 describes the preparation of silicafluorided with a fluoriding agent at room temperature for comparison asa support to fluorided silica of the present invention.

Comparative Example 7

[0217] 15.0 grams of 952 silica gel, previously heat dehydrated with theheat schedule shown in Example 1, was loaded into a 250 milliliter flaskand the flask evacuated. The vacuum was replaced by N₂ and the procedurerepeated three times. In the dry box under N₂ a stir bar was added. In aseparate flask 42.25 grams of dry and N₂ purged toluene was combinedwith 0.615 grams dimethylamine sulfur trifluoride, available fromAldrich Chemical Co. The toluene solution was slowly added to the silicathen the slurry was heated to 50° C. for 150 minutes followed by moretoluene (15.1 grams) and an additional 30 minutes heating. Stirring wasstopped and the supernatant decanted. The residue was washed three timeswith 20-25 gram portions of toluene. The final residue was vacuum driedto a final temperature of 60° C. Dry weight of the treated silica was15.35 grams. Neutron Activation Analysis showed 1.70±0.1 percentfluorine. The fluorided silica was stored under N₂ prior to use.

[0218] The Comparative Examples 8-10 show that silica gel can behalogenated with the congeners of fluorine during heat dehydration.

Comparative Examples 8 through 10

[0219] In a manner similar to Example 15, non-fluorided silica (952silica gel) was mixed with other ammonium halide compounds in molaramounts equal to the millimoles fluorine used then the mixture washeated as described previously. When cool the dehydrated silicas werestored under N₂.

[0220] Details are shown in Table 3. Column three describes the wt % ofhalide compound present in the total silica/halide compound sample.Column four labeled “added” describes the wt % of halide present in thesample before heating. Column five labeled “found” describes the wt % ofhalide present in the sample after heating. TABLE 3 Treated withCongener Halogens wt %¹ of Comparative Halide Elemental Halide (wt %)Example Halide Compound Compound Added¹ Found 8 NH₄Cl 5.3 3.7  0.19 ±0.004 9 NH₄Br 9.3 8.4 0.38 ± 0.04 10  NH₄I 13.4  13.5  0.36 ± 0.03

[0221] Catalysts

[0222] Examples 24-25 and Comparative Examples 11-12 show thatmetallocene catalysts prepared with methylalumoxane and dehydratedfluorided silica as the support have higher activity compared to thesame catalysts prepared with methylaumoxane using dehydrated silica.Except as otherwise stated in the specific example, the polymerizationprocedure of Example 24 was followed.

Example 24

[0223] In the dry box under N₂ 0.0525 grams ofrac-dimethylsilandiylbis(2-methylindenyl) zirconium dichloride wasplaced in a 50 milliliter beaker and 4.55 grams of Methylalumoxane as a30% solution in toluene was added. The resulting metallocene solutionwas stirred for 30 minutes with a bar magnet. Then 15.0 grams of driedand N₂ purged toluene was added followed by another 5 minutes ofstirring. Separately 5.00 grams of the fluorided silica prepared inExample 8 was transferred to a 150 milliliter beaker. The metallocenesolution was added to the fluorided silica gel in three aliquots withstirring. The resulting slurry was stirred for an additional 60 minutesthen the volatiles were removed under vacuum. Heat was applied to thedrying catalyst until a final temperature of 50° C. was held for 60minutes. The dried catalyst was 6.52 grams of a finely divided, freeflowing solid. Elemental analysis showed 9.18% Al and 0.142% Zr.

[0224] Batch Polymerization

[0225] A 2 liter autoclave reactor previously hot flushed with N₂ andcooled to ambient temperature was charged with triethylaluminum (1milliliter of a 1M solution in hexane) followed by 1100 milliliters ofpropylene. If needed for the polymerization about 5 millimole hydrogenwas added from a reservoir by pressure difference prior to thepropylene. After heating the reactor contents to 70° C. 100 milligramscatalyst solid, slurried in 2 milliliters of hexane, was flushed in with100 milliliters of propylene to start the reaction. After one hour, thereactor was cooled, vented, purged with N₂ for 20 minutes and thenopened. The polypropylene was transferred to a glass dish and allowed todry in a fume hood overnight. The next day the polymer was further driedin vacuo at 75° C. for one hour. The dried polymer was weighed.

[0226] Polymer Analysis: MFR was measured by the method of ASTM-1238Condition L. Apparent Density is measured using the method of ASTMD-1895-89 Method A. Particle Size was measured by the method of ASTM D1921-89 Method A. Molecular Weight (MW) and its distribution (MWD) wasmeasured by GPC on a Waters 150-C at 145° C. using1,2,4-trichlorobenzene as the solvent.

[0227] 106.8 milligram of the solid prepared as described in Example 24gave 334.1 grams polypropylene in 60 minutes. Productivity was 3128 g PPg catalyst. Activity was 200.9 Kg PP/millimole Zr. Analysis showed thepolymer to have the following properties: 25.8 MFR, 149532 g/mole MW and1.82 dispersity.

Example 25

[0228] In the dry box under N₂ 0.0705 grams ofrac-dimethylsilandiylbis(2-methyl-4-phenyl-1-indenyl) zirconiumdichloride was placed in a 50 milliliter beaker and 4.55 grams ofMethylalumoxane as a 30% solution in toluene was added. The resultingmetallocene solution was stirred for 30 minutes with a bar magnet. Then14.0 grams of dried and N₂ purged toluene was added followed by another5 minutes of stirring. Separately 5.00 grams of the fluorided silicaprepared in Example 8 was transferred to a 150 milliliter beaker. Themetallocene solution was added to the fluorided silica gel in threealiquots with stirring. The resulting slurry was stirred for anadditional 60 minutes then the volatiles were removed under vacuum. Heatwas applied to the drying catalyst until a final temperature of 50° C.was held for 60 minutes. The dried catalyst was 6.48 grams of a finelydivided, free flowing solid. Elemental analysis showed 9.55% Al and0.153% Zr. 109.8 milligram of the solid gave 326.3 grams polypropylenein 60 minutes. Productivity was 2972 g PP/g catalyst. Activity was 177.2Kg PP/millimole Zr. Analysis showed the polymer to have the followingproperties: 577822 g/mole MW and 2.12 dispersity.

Comparative Example 11

[0229] In the dry box under N₂ 0.0532 grams ofrac-dimethylsilandiylbis(2-methylindenyl) zirconium dichloride wasplaced in a 50 milliliter beaker and 4.56 grams of Methylalumoxane as a30% solution in toluene was added. The resulting metallocene solutionwas stirred for 30 minutes with a bar magnet. Then 16.5 grams of driedand N₂ purged toluene was added followed by another 5 minutes ofstirring. Separately 5.00 grams of the silica prepared in ComparativeExample 3 was transferred to a 150 milliliter beaker. The metallocenesolution was added to the silica gel in three aliquots with stirring.The resulting slurry was stirred for an additional 60 minutes then thevolatiles were removed under vacuum. Heat was applied to the dryingcatalyst until a final temperature of 50° C. was held for 60 minutes.The dried catalyst was 6.67 grams of a finely divided, free flowingsolid. Elemental analysis showed 9.12% Al and 0.128% Zr. 102.7 milligramof the solid gave 111.2 grams polypropylene in 60 minutes. Productivitywas 1083 g PP/g catalyst. Activity was 77.2 Kg PP/millimole Zr. Analysisshowed the polymer to have the following properties: 23.4 MFR, 143867g/mole MW and 1.72 dispersity.

Comparative Example 12

[0230] In the dry box under N₂ 0.0709 grams ofrac-dimethylsilandiylbis(2-methyl-4-phenyl-1-indenyl) zirconiumdichloride was placed in a 50 milliliter beaker and 4.56 grams ofMethylalumoxane as a 30% solution in toluene was added. The resultingmetallocene solution was stirred for 30 minutes with a bar magnet. Then16.5 grams of dried and N₂ purged toluene was added followed by another5 minutes of stirring. Separately 5.00 grams of the silica prepared inComparative Example 3 was transferred to a 150 milliliter beaker. Themetallocene solution was added to the silica gel in three aliquots withstirring. The resulting slurry was stirred for an additional 60 minutesthen the volatiles were removed under vacuum. Heat was applied to thedrying catalyst until a final temperature of 50° C. was held for 60minutes. The dried catalyst was 6.48 grams of a finely divided, freeflowing solid. Elemental analysis showed 9.19% Al and 0.120% Zr. 103.3milligram of the solid gave 82.9 grams polypropylene in 60 minutes.Productivity was 803 g PP/g catalyst. Activity was 61.0 Kg PP/millimoleZr. Analysis showed the polymer to have the following properties: 689094g/mole MW and 2.17 dispersity.

[0231] Comparison of the results detailed above shows that thedehydrated fluorided silica catalyst has more than double the activityof the dehydrated silica catalyst based on Zr contained.

[0232] The following examples show that metallocene catalysts preparedwith a non-coordinating anion and using dehydrated fluorided silica asthe support have higher activity compared to the same catalysts preparedusing dehydrated silica.

Example 26

[0233] In the dry box under N₂ 5.00 grams of the fluorided silicaprepared in Example 4 was transferred to a 250 milliliter flaskcontaining a bar magnet. In a 50 milliliter beaker 0.18 gramsN,N′-diethylaniline, available from Aldrich Chemical Company, MilwaukeeWis. was diluted with 18.0 milliliters of dried and N₂ purged hexane.This solution was added slowly to the silica with stirring to form athick slurry. The slurry was diluted with 5.0 milliliters of hexane andheat applied as stirring continued. At the end of 30 minutes thetemperature was 40° C. 0.55 grams of tris-perfluorophenylborane,available from Boulder Scientific Company, Mead, Colo. was added and thestirring—heating continued. After an additional 60 minutes thetemperature was constant at 50° C. 0.06 grams ofrac-dimethylsilandiylbis(2-methylindenyl) zirconium dimethyl was addedand the stirring—heating continued. After 120 minutes heating wasstopped and the slurry was permitted to settle. The supernatant wasremoved and the solids were dried under vacuum. Heat was applied as thecatalyst dried until a final temperature of 30° C. was held for 60minutes. The dried catalyst was 5.85 grams of a finely divided, freeflowing solid. Elemental analysis showed 0.20% B and 0.21% Zr. 105.0milligram of the solid gave 135.7 grams polypropylene in 60 minutes.Productivity was 1292 g PP/g catalyst. Activity was 56.1 Kg PP/millimoleZr. Analysis showed the polymer to have the following properties: 105024g/mole MW and 1.96 dispersity.

Example 27

[0234] 101.2 milligrams of the catalyst prepared in Example 26 wascharged to the polymerization reactor containing hydrogen. 127.6 gramspolypropylene was prepared in 60 minutes. Productivity was 1261 g PP/gcatalyst. Activity was 54.8 Kg PP/millimole Zr. Analysis showed thepolymer to have the following properties: 107642 g/mole MW and 2.03dispersity.

Comparative Example 13

[0235] In a manner similar to Example 26 a catalyst was prepared exceptthe silica of Comparative Example 3 was used. The dried catalyst was5.75 grams of a finely divided, free flowing solid. Elemental analysisshowed 0.19% B and 0.22% Zr. 103.6 milligram of the solid gave 8.7 gramspolypropylene in 60 minutes. Productivity was 84 g PP/g catalyst.Activity was 3.5 Kg PP/millimole Zr. Analysis showed the polymer to havethe following properties: 102315 g/mole MW and 2.04 dispersity.

Comparative Example 14

[0236] 99.2 milligrams of the catalyst prepared in Comparative Example13 was charged to the polymerization reactor containing hydrogen. 13.6grams polypropylene was prepared in 60 minutes. Productivity was 137 gPP/g catalyst. Activity was 5.7 Kg PP/millimole Zr. Analysis showed thepolymer to have the following properties: 91845 g/mole MW and 1.90dispersity.

[0237] Comparison of the results detailed above shows that thedehydrated fluorided silica catalyst has on average about 1280 percentmore activity than the dehydrated silica catalyst on a Zr basis.

Example 28

[0238] In the dry box under N₂ 5.01 grams of the fluorided silicaprepared in Example 4 was transferred to a 250 milliliter flaskcontaining a bar magnet. In a 50 milliliter beaker 0.18 gramsN,N′-diethylaniline, available from Aldrich Chemical Company, MilwaukeeWis. was diluted with 18.0 milliliters of dried and N₂ purged hexane.This solution was added slowly to the silica with stirring to form athick slurry. The slurry was diluted with 5.0 milliliters of hexane andheat applied as stirring continued. At the end of 30 minutes thetemperature was 40° C. 0.55 grams of tris-perfluorophenylborane,available from Boulder Scientific Company, Mead, Colo. was added and thestirring—heating continued. After an additional 60 minutes thetemperature was constant at 50° C. 0.08 grams ofrac-dimethylsilandiylbis(2-methyl-4-phenyl-1-indenyl) zirconium dimethylwas added and the stirring—heating continued. After 120 minutes heatingwas stopped and the slurry was permitted to settle. The supernatant wasremoved and the solids were dried under vacuum. Heat was applied as thecatalyst dried until a final temperature of 30° C. was held for 60minutes. The dried catalyst was 5.84 grams of a finely divided, freeflowing solid. Elemental analysis showed 0.22% B and 0.21% Zr. 101.6milligram of the solid gave 155.3 grams polypropylene in 60 minutes.Productivity was 1529 g PP/g catalyst. Activity was 66.4 Kg PP/millimoleZr. Analysis showed the polymer to have the following properties: 529068g/mole MW and 2.35 dispersity.

Example 29

[0239] 102.5 milligrams of the catalyst prepared in Example 28 wascharged to the polymerization reactor containing hydrogen. 237.0 gramspolypropylene was prepared in 60 minutes. Productivity was 2312 g PP/gcatalyst. Activity was 100.4 Kg PP/millimole Zr. Analysis showed thepolymer to have the following properties: 474587 g/mole MW and 2.48dispersity.

Comparative Example 15

[0240] In a manner similar to Example 28 a catalyst was prepared exceptthe silica of Comparative Example 3 was used. The dried catalyst was5.90 grams of a finely divided, free flowing solid. Elemental analysisshowed 0.19% B and 0.18% Zr. 100.1 milligram of the solid gave 22.0grams polypropylene in 60 minutes. Productivity was 220 g PP/g catalyst.Activity was 11.1 Kg PP/millimole Zr. Analysis showed the polymer tohave the following properties: 579479 g/mole MW and 2.40 dispersity.

Comparative Example 16

[0241] 105.1 milligrams of the catalyst prepared in Comparative Example15 was charged to the polymerization reactor containing hydrogen. 120.7grams polypropylene was prepared in 60 minutes. Productivity was 1148 gPP/g catalyst. Activity was 58.2 Kg PP/millimole Zr. Analysis showed thepolymer to have the following properties: 529068 g/mole MW and 2.35dispersity.

[0242] Comparison of the results detailed above shows that thedehydrated fluorided silica catalyst has on average about 380 percentmore activity on a Zr basis than the dehydrated silica catalyst.

[0243] The following examples show that metallocene catalysts preparedwith a non-coordinating anion and using other dehydrated fluoridedsilicas as the support also show high activity compared to the similarcatalysts prepared using dehydrated silicas.

Example 30

[0244] In the dry box under N₂ 5.00 grams of the fluorided silicaprepared in Example 2 was transferred to a 250 milliliter flaskcontaining a bar magnet. In a 50 milliliter beaker 0.18 gramsN,N′-diethylaniline, available from Aldrich Chemical Company, MilwaukeeWis. was diluted with 18.0 milliliters of dried and N₂ purged hexane wasadded. This solution was added slowly to the silica with stirring toform a thick slurry. The slurry was diluted with 5.0 milliliters ofhexane and heat applied as stirring continued. At the end of 30 minutesthe temperature eas 40° C. 0.55 grams of tris-perfluorophenylborane,available from Boulder Scientific Company, Mead, Colo. was added and thestirring—heating continued. After an additional 60 minutes thetemperature was constant at 50° C. 0.08 grams ofrac-dimethylsilandiylbis(2-methyl-4-phenyl-1-indenyl) zirconium dimethylwas added and the stirring—heating continued. After 120 minutes heatingwas stopped and the slurry was permitted to settle. The supernatant wasremoved and the solids were dried under vacuum. Heat was applied as thecatalyst dried until a final temperature of 30° C. was held for 60minutes. The dried catalyst was 5.69 grams of a finely divided, freeflowing solid. Elemental analysis showed 0.22% B and 0.18% Zr.

Examples 31 through 39

[0245] In a manner similar to Example 30 catalysts were prepared onother 500° C. fluorided silicas. The details are shown in Table 4. Thepolymerization shown in Tables 5 and 6. TABLE 4 Catalysts Prepared on500° C. Fluorided Silicas Fluorided Elemental Catalyst Silica Loading¹Analysis Example Example B Zr % B % Zr 31 3 0.21 0.026 0.18 0.18 32 5 ″″ 0.18 0.17 33 6 ″ ″ n.d. n.d. 34 7 ″ ″ 0.16 0.12 35 8 0.22 0.028 0.370.22 36 8 0.13 0.027 0.35 0.21 37 11 0.21 ″ 0.19 0.19 38 11 0.13 ″ 0.130.22 39 14 0.21 0.026 0.23 0.24

[0246] TABLE 5 Polymerization Results for Catalyst on 500° C. FluoridedSilicas Productivity Activity Catalyst (g PP/g Catalyst- (Kg PP/mM Zr-Example Hr) Hr) 31 555 24.8 32 3267 136.5 33 723 30.6 34 49 2.1 35 3330133.3 36 3258 135.4 37 780 33.4 38 490 20.5 39 725 32.9

[0247] TABLE 6 Polymerization Results for Catalyst on 500° C. FluoridedSilicas¹ Productivity Activity Catalyst (g PP/g Catalyst- (Kg PP/mM Zr-Example Hr) Hr) 31 2083 93.1 32 3353 140.1 33 919 38.8 34 365 15.5 355180 207.3 36 3496 145.3 37 2004 85.8 38 1820 76.0 39 2435 110.7

Examples 40 through 47

[0248] In a manner similar to Example 30 catalysts were prepared onother 300° C. fluorided silicas. The details are shown in Table 7. Thepolymerization results are shown in table 8 and 9. TABLE 7 CatalystsPrepared on 300° C. Fluorided Silicas Fluorided Elemental CatalystSilica Loading¹ Analysis Example Example B Zr % B % Zr 40 17 0.21 0.0260.20 0.22 41 18 ″ ″ 0.18 0.20 42 16 ″ 0.027 0.22 0.19 43 16 0.13 ″ 0.110.19 44 19 0.21 ″ 0.21 0.20 45 20 ″ ″ 0.13 0.16 46 20 0.13 ″ 0.09 0.2047 21 0.21 0.026 0.37 0.21

[0249] TABLE 8 Polymerization Results for Catalysts on 300° C. FluoridedSilicas Productivity Actvity Catalyst (gPP/g Catalyst- (Kg PP/mM Zr-Example Hr) Hr) 40 310 13.4 41 1041 45.2 42 511 22.0 43 615 25.3 44 2655113.5 45 2897 119.7 46 1927 77.0 47 428 18.6

[0250] TABLE 9 Polymerization Results for Catalysts on 300° C. FluoridedSilicas¹ Productivity Activity Catalyst (g PP/g Catalyst- (Kg PP/mM Zr-Example Hr) Hr) 40 1150 49.8 41 1125 48.8 42 1433 61.6 43 1172 48.2 442603 111.2 45 3060 126.4 46 2603 111.2 47 1137 49.4

Comparative Examples 17 through 23

[0251] In a manner similar to Example 30 catalysts were prepared exceptdehydrated silicas were used. The details are shown in Table 10. Thepolymerization results are shown in Tables 11 and 12. TABLE 10 CatalystsPrepared on Dehydrated Silicas Catalyst Dehydrated Comp. Silica Loading¹Elemental Analysis Example Comp. Example B Zr % B % Zr 17 1 0.12 0.0140.14 0.11 18 2 0.43 0.027 0.35 0.19 19 2 0.21 ″ 0.21 0.22 20 3 ″ 0.0260.19 0.18 21 3 0.13 0.027 0.11 0.20 22 5 0.21 0.026 0.21 0.22 23 5 0.130.027 0.11 0.21

[0252] TABLE 11 Polymerization Results for Catalysts on DehydratedSilicas Catalyst Productivity Activity Comp. (g PP/g Catalyst- (Kg PP/mMZr- Example Hr) Hr) 18 400 19.4 19 258 11.3 20 220 9.6 21 165 7.0 22 1446.4 23  85 3.7

[0253] TABLE 12 Polymerization Results for Catalysts on DehydratedSilicas¹ Catalyst Productivity Activity Comp. (g PP/g Catalyst- (KgPP/mM Zr- Example Hr) Hr) 17 504 41.8 18 357 17.1 19 621 27.2 20 1148 52.0 21 768 32.4 22 495 22.1 23 541 23.5

[0254] The following example shows that a metallocene catalyst preparedwith a non-coordinating anion on a chemically dehydrated silica does nothave the high activity of a similar catalyst prepared on a fluorideddehydrated silica.

Comparative Example 24

[0255] In a manner similar to Example 30 catalyst was prepared exceptthe hexamethyldisilazane treated silica of Comparative Example 6 wasused. The dried catalyst was 6.70 grams of a finely divided, freeflowing solid. Elemental analysis showed 0.29% B and 0.17% Zr. 100.8milligram of the solid gave 6.7 grams polypropylene in 60 minutes.Productivity was 66.5 g PP/g catalyst. Activity was 3.6 Kg PP/millimoleZr.

[0256] The following example shows that a metallocene catalyst preparedwith a non-coordinating anion on an alternately fluorided silica doesnot have the high activity of a similar catalyst prepared on a fluorideddehydrated silica.

Comparative Example 25

[0257] In a manner similar to Example 30 catalyst was prepared exceptthe dimethylamine sulfur trifluoride treated silica of ComparativeExample 7 was used. The dried catalyst was 5.36 grams of a finelydivided, free flowing solid. Elemental analysis showed 0.095% B and0.096% Zr. 98.7 milligram of the solid was added to the polymerizationreactor to test activity. The solid was inactive for propylenepolymerization.

[0258] The following examples show that metallocene catalysts preparedwith a non-coordinating anion on a dehydrated silica halogenated withthe congeners of fluorine do not have the high activity of a similarcatalyst prepared on a dehydrated fluorided silica.

Comparative Example 26

[0259] In a manner similar to Example 30 catalyst was prepared exceptthe ammonium chloride halogenated silica of Comparative Example 8 wasused. The dried catalyst was 5.52 grams of a finely divided, freeflowing solid. Elemental analysis showed 0.12% B and 0.11% Zr. 99.3milligram of the solid was added to the polymerization reactor to testactivity. The solid was inactive for propylene polymerization.

Comparative Example 27

[0260] In a manner similar to Example 30 catalyst was prepared exceptthe ammonium bromide halogenated silica of Comparative Example 9 wasused. The dried catalyst was 5.61 grams of a finely divided, freeflowing solid. Elemental analysis showed 0.11% B and 0.16% Zr. 99.7milligram of the solid was added to the polymerization reactor to testactivity. The solid was inactive for propylene polymerization.

[0261] The following Examples show that the advantages of usingfluorided silica as a catalyst support are not lost or diminished whenlarger quantities are fluorided nor is the high activity of theresulting catalysts compromised when a continuous polymerization processis used.

Example 48

[0262] A fluorided silica was prepared by Grace Davison fromSylopol®9522 and ammonium hexafluorosilicate according to the procedureof Example 1. Elemental analysis showed the fluorine content to be1.49±0.06% by weight. Moreover the fluorided silica gel had thefollowing properties: 1.69 cc/g pore volume, 256 m²/g surface area and35 microns average particle size. In the dry box under N₂ 401 grams ofthis silica was transferred to a 4 liter flask. 6.4 gramsN,N′-diethylaniline was combined with 1542 grams dried and N₂ spargedhexane . All the liquid was added to the silica. The slurry wasmechanically stirred and heat applied. After 30 minutes 21.61 gramstris-perfluorophenylborane was added. After 60 minutes 3.20 grams ofrac-dimethylsilandiylbis(2-methyl-4-phenyl-1-indenyl) zirconium dimethylwas added. The slurry temperature was 50 ° C. During the next 120minutes stirring continued and a final temperature of 51 ° C. wasreached. At this time heating was stopped and the slurry was permittedto settle. The clear, colorless supernatant was removed and found tohave less than 4 PPM Zirconium or Boron and 6 PPM N. The total amount ofsupernatant removed before drying was 575.4 grams. The solids were driedunder vacuum. Heat was applied as the catalyst dried until the freeflowing solid was held at a final temperature of 30° C. for 120 minutes.The dried catalyst was 423.8 grams. Elemental analysis showed 0.101% Band 0.114% Zr. 102.6 milligram of the solid was charged to thepolymerization batch reactor at 70° C. along with about 5 millimole H₂.Yield was 199 grams polypropylene in 35 minutes. Productivity per hourwas 3326 g PP/g catalyst. Activity per hour was 266 Kg PP/millimole Zr.Analysis showed the polymer to have the following properties: 0.42 g/mlapparent density, 352052 g/mole MW and 2.34 dispersity.

Example 48A Continuous Polymerization

[0263] The polymerization was conducted in liquid propylene, in a pilotscale polymerization process employing two reactors in series. Thereactors were equipped with jackets for removing the heat ofpolymerization. The reactor temperature was set at 74° C. in the firstreactor and 68° C. in the second reactor. The catalyst prepared asdescribed above was fed at a rate of 1-2 g/hr. A 1 wt % TEAL in hexanesolution was fed at a rate of 4-5 cc/min. Propylene was fed at a rate ofabout 80 kg/hr to the first reactor and about 27 kg/hr to the secondreactor. Hydrogen concentration in the first reactor was 1000 mppm and1300 mppm in the second. Residence times were about 2.5 hours in thefirst reactor and about 1.9 hours in the second reactor. The productionrate of polymer from the reactors was about 40 kg/hr. CatalystProductivity was calculated from the total weight of polymer made andthe total weight of catalyst used. Productivity for Catalyst of Example48 was 20.5 Kg/g catalyst and activity was 1639 Kg/millimole Zr. Thepolymer was discharged from the reactors as a granular product havingthe following properties: 2.62 MFR, apparent density of 0.46 g/cm³ andaverage particle size of 999.3 microns.

Examples 49 through 52

[0264] Examples 49 through 52 were generated in a manner similar to thecontinuous polymerization described in Example 48A,except thatpolymerization was allowed to occur at various levels of hydrogen. Thedata are shown in Table 13. TABLE 13 Continuous Polymerization Resultsfor Catalyst Example 48 H₂ H₂ Produc- Reactor Reactor tivity 1 2 (Kg/gAD APS Example (mppm)¹ (mppm) catalyst) MFR (g/cm³) (microns) 49 22002900 27.0 17.4 0.45 981.2 50 2500 3150 25.8 25.8 0.47 1001.0 51 44005050 22.0 172.5 0.45 925.5 52 7300 8800 15.2 1324 0.45 848.0

[0265] The following Examples show that the advantages of usingfluorided silica as a catalyst support are reproducible.

Example 53

[0266] A second fluorided silica was prepared by Grace Davison fromSylopol®9522 and ammonium hexafluorosilicate according to the heatschedule of Example 1. Elemental analysis showed the fluorine content tobe 2.35±0.05% by weight. The fluorided silica gel had the followingproperties: 1.62 cc/g pore volume, 243 m²/g surface area and 39 micronsaverage particle size. In the dry box under N₂ 465.4 grams of thissilica was transferred to a 4 liter flask. 7.5 grams N,N′-diethylanilinewas combined with 1800grams dried and N₂ sparged hexane . All the liquidwas added to the silica. The slurry was mechanically stirred and heatapplied. At the 30 minute mark the temperature was 50.8° C. and 25.2grams tris-perfluorophenylborane was added. After 60 minutes thetemperature was 53° C. and 3.70 grams ofrac-dimethylsilandiylbis(2-methyl-4-phenyl-1-indenyl) zirconium dimethylwas added. During the next 120 minutes stirring continued and a finaltemperature of 55° C. was reached. At this time heating was stopped andthe slurry was permitted to settle. The clear, colorless supernatant wasremoved and found to weigh 404.7 grams. The solids were dried undervacuum. Heat was applied as the catalyst dried until the free flowingsolid was held at a final temperature of 35° C. for 120 minutes. Thedried catalyst was 486.93 grams. Elemental analysis showed 0.10% B and0.11% Zr.

Examples 54 through 58

[0267] Using the supported catalyst of Example 53, a series of batchpolymerization runs were made as described in Example 48. The resultsare shown in Table 14. TABLE 14 Batch Polymerization Results forCatalyst Example 53¹ Time Productivity/Hr AD APS Example (hr) (Kg/gcatalyst-hr) MFR (g/cm³) (microns) 54 0.5 5305 n.d.² 0.34 849 55 1.04917 97 0.41 570 56 1.0 5146 88 0.40 678 57 1.0 6012 14 0.38 734 58 2.03466 53 0.40 702

Examples 59 through 62

[0268] Using the supported catalyst described in Example 53, a series ofcontinuous polymerization runs, as described in Example 48A, were made.The data are shown in Table 15. TABLE 15 Continuous PolymerizationResults for Catalyst Example 53 H₂ H₂ Productivity Activity Reactor 1Reactor 2 (Kg/g (Kg/mM AD APS Example (mppm)¹ (mppm) catalyst) Zr) MFR(g/cm³) (microns) 59 2500 3200 46.3 3880.7 11.4 0.43 1219 60 2600 360055.0 4601.9 15.8 0.47 1019 61 3300 3800 44.8 3748.9 27.8 0.46 1077 623700 4300 46.2 3872.1 37.1 0.47 1144

[0269] Discussion

[0270] Although the above Examples deal primarily with metallocenesupported catalyst composition, it will be recognized that theattributes of the polymers produced by the metallocene supportedcatalyst composition of the present invention will lend themselves touse in end-product applications. Examples of such end-productapplications include, articles made from films, thermoforming and blowmolding, fibers, such as meltblown fibers and spunbond fibers, andfabrics.

[0271] While the present invention has been described and illustrated byreference to particular embodiments, it will be appreciated by those ofordinary skill in the art that the invention lends itself to manydifferent variations not illustrated herein. For these reasons, then,reference should be made solely to the appended claims for purposes ofdetermining the true scope of the present invention.

[0272] Although the appendant claims have single appendencies inaccordance with U.S. patent practice, each of the features in any of theappendant claims can be combined with each of the features of otherappendant claims or the main claim.

The following is claimed:
 1. A metallocene supported catalystcomposition comprising: a metallocene catalyst; and a supportcomposition represented by a formula Sup F wherein Sup is a support andF is a fluorine atom bound to the support.
 2. The metallocene supportedcatalyst composition of claim 1 wherein the metallocene catalyst isrepresented by a formula: Cp_(m)MR_(n)X_(q) wherein Cp is acyclopentadienyl ring which may be substituted, or derivative thereofwhich may be substituted, M is a Group 4, 5, or 6 transition metal, R isa hydrocarbyl group or hydrocarboxy group having from one to 20 carbonatoms, X may be a halide, a hydride, an alkyl group, an alkenyl group oran arylalkyl group and m=1-3, n=0-3, q=0-3, and the sum of m+n+q isequal to the oxidation state of the transition metal.
 3. A metallocenesupported catalyst composition comprising: a metallocene catalyst; and asupport composition represented by a formula Sup L F_(n) wherein Sup isa support selected from the group consisting of talc, clay, silica,alumina, magnesia, zirconia, iron oxides, boria, calcium oxide, zincoxide, barium oxide thoria, aluminum phosphate gel, polyvinylchloride orsubstituted polystyrene; “L” is a first member selected from the groupconsisting of (i) bonding, sufficient to bound the F to the Sup; (ii) B,Ta, Nb, Ge, Ga, Sn, Si, P, Ti, Mo, Re, or Zr bound to the Sup and to theF; or (iii) 0 bound to the Sup and bound to a second member selectedfrom the group consisting of B, Ta, Nb, Ge, Ga, Sn, Si, P, Ti, Mo, Re,or Zr which is bound to the F; “F” is a fluorine atom; and “n” is anumber from 1-7.
 4. The metallocene supported catalyst composition ofclaim 3 wherein the support composition is a fluorided supportcomposition.
 5. The metallocene supported catalyst composition of claim3 wherein the metallocene catalyst is represented by a formula:Cp_(m)MR_(n)X_(q) wherein Cp is a cyclopentadienyl ring which may besubstituted, or derivative thereof which may be substituted, M is aGroup 4, 5, or 6 transition metal, R is a hydrocarbyl group orhydrocarboxy group having from one to 20 carbon atoms, X may be ahalide, a hydride, an alkyl group, an alkenyl group or an arylalkylgroup , and m=1-3, n=0-3, q=0-3, and the sum of m+n+q is equal to theoxidation state of the transition metal.
 6. The metallocene supportedcatalyst composition of claim 3 further including an activator.
 7. Themetallocene supported catalyst composition of claim 6 wherein theactivator is an alkylalumoxane.
 8. The metallocene supported catalystcomposition of claim 6 wherein the activator is a noncoordinating anionactivator.
 9. The metallocene supported catalyst composition of claim 3wherein the metallocene is selected from the group consisting of:Dimethylsilandiylbis (2-methyl-4-phenyl-1-indenyl)Zirconium dimethylDimethylsilandiylbis(2-methyl-4,5-benzoindenyl) Zirconium dimethyl;Dimethylsilandiylbis(2-methyl-4,6-diisopropylindenyl) Zirconiumdimethyl; Dimethylsilandiylbis(2-ethyl-4-phenyl-1-indenyl) Zirconiumdimethyl; Dimethylsilandiylbis(2-ethyl-4-naphthyl-1-indenyl) Zirconiumdimethyl, Dimethylsilandiylbis(2-methyl-4-(1-naphthyl)-1-indenyl)Zirconium dimethyl,Dimethylsilandiylbis(2-methyl-4-(2-naphthyl)-1-indenyl) Zirconiumdimethyl, Dimethylsilandiylbis(2-methyl-indenyl) Zirconium dimethyl,Dimethylsilandiylbis(2-methyl-4,5-diisopropyl-1-indenyl) Zirconiumdimethyl, Dimethylsilandiylbis(2,4,6-trimethyl-1-indenyl) Zirconiumdimethyl, Dimethylsilandiylbis(2-methyl-1-indenyl) Zirconium dimethyl,Dimethylsilandiylbis(2-ethyl-1-indenyl) Zirconium dimethyl,Dimethylsilandiylbis(2,5,6-trimethyl-1-indenyl) Zirconium dimethyl,Dimethylsilandiylbis(2-methyl-4-phenyl-1-indenyl)Zirconium dichlorideDimethylsilandiylbis(2-methyl-4,5-benzoindenyl) Zirconium dichloride;Dimethylsilandiylbis(2-methyl-4,6-diisopropylindenyl) Zirconiumdichloride; Dimethylsilandiylbis(2-ethyl-4-phenyl-1-indenyl) Zirconiumdichloride; Dimethylsilandiylbis(2-ethyl-4-naphthyl-1-indenyl) Zirconiumdichloride, Dimethylsilandiylbis(2-methyl-4-(1-naphthyl)-1-indenyl)Zirconium dichloride,Dimethylsilandiylbis(2-methyl-4-(2-naphthyl)-1-indenyl) Zirconiumdichloride, Dimethylsilandiylbis(2-methyl-indenyl) Zirconium dichloride,Dimethylsilandiylbis(2-methyl-4,5-diisopropyl-1-indenyl) Zirconiumdichloride, Dimethylsilandiylbis(2,4,6-trimethyl -1-indenyl) Zirconiumdichloride, Dimethylsilandiylbis(2-methyl-1-indenyl) Zirconiumdichloride, Dimethylsilandiylbis(2-ethyl-1-indenyl) Zirconiumdichloride, or Dimethylsilandiylbis(2,5,6-trimethyl-1-indenyl) Zirconiumdichloride.
 10. The metallocene supported catalyst composition of claim3 wherein the fluorine concentration is in the range of from 0.01 to10.0 millimoles of fluorine per gram of support.
 11. A method of makinga metallocene supported catalyst composition comprising the step of:contacting a metallocene catalyst with a support composition undersuitable conditions and for a sufficient time, wherein the supportcomposition is represented by a formula Sup L F_(n) wherein Sup is asupport selected from the group consisting of talc, clay, silica,alumina, magnesia, zirconia, iron oxides, boria, calcium oxide, zincoxide, barium oxide thoria, aluminum phosphate gel, polyvinylchlorideand substituted polystyrene; “L” is a first member selected from thegroup consisting of (i) bonding, sufficient to bound the F to the Sup;(ii) B, Ta, Nb, Ge, Ga, Sn, Si, P, Ti, Mo, Re, or Zr bound to the Supand to the F; or (iii) O bound to the Sup and bound to a second memberselected from the group consisting of B, Ta, Nb, Ge, Ga, Sn, Si, P, Ti,Mo, Re, or Zr which is bound to the F; “F” is a fluorine atom; and “n”is a number from 1-7.
 12. The method of claim 11 comprising the step ofcontacting the metallocene catalyst with an activator before contactingthe metallocene with the support composition.
 13. The method of claim 11wherein the support composition is a fluorided support composition. 14.A polymerization method comprising the step of: contacting apolymerizable olefin with a metallocene supported catalyst compositionunder suitable conditions and for a sufficient time wherein themetallocene supported catalyst composition comprises a metallocenecatalyst; a support composition represented by a formula Sup L F_(n)wherein Sup is a support selected from the group consisting of talc,clay, silica, alumina, magnesia, zirconia, iron oxides, boria, calciumoxide, zinc oxide, barium oxide thoria, aluminum phosphate gel,polyvinylchloride and substituted polystyrene; “L” is a first memberselected from the group consisting of (i) bonding, sufficient to boundthe F to the Sup; (ii) B, Ta, Nb, Ge, Ga, Sn, Si, P, Ti, Mo, Re, or Zrbound to the Sup and to the F; or (iii) 0 bound to the Sup and bound toa second member selected from the group consisting of B, Ta, Nb, Ge, Ga,Sn, Si, P, Ti, Mo, Re, or Zr which is bound to the F; “F” is a fluorineatom; and “n” is a number from 1-7.
 15. The method of claim 14 whereinthe polymerizable olefin is propylene.
 16. An article incorporating apolymer product of claim
 14. 17. The article of claim 16 comprising amember selected from the group consisting of films, fibers, fabrics, andmolded structures.
 18. The method of claim 14 wherein the supportcomposition is a fluorided support composition.
 19. A metallocenesupported catalyst composition consisting essentially of: one or moremetallocene catalyst; activator; and a support composition representedby a formula Sup L F_(n) wherein Sup is a support selected from thegroup consisting of talc, clay, silica, alumina, magnesia, zirconia,iron oxides, boria, calcium oxide, zinc oxide, barium oxide thoria,aluminum phosphate gel, polyvinylchloride or substituted polystyrene andmixtures thereof; “L” is a first member selected from the groupconsisting of (i) bonding, sufficient to bound the F to the Sup; (ii) B,Ta, Nb, Ge, Ga, Sn, Si, P, Ti, Mo, Re, or Zr bound to the Sup and to theF; or (iii) 0 bound to the Sup and bound to a second member selectedfrom the group consisting of B, Ta, Nb, Ge, Ga, Sn, Si, P, Ti, Mo, Re,or Zr which is bound to the F; “F” is a fluorine atom; and “n” is anumber from 1-7.
 20. The metallocene supported catalyst composition ofclaim 19 wherein the support composition is a fluorided supportcomposition.
 21. The metallocene supported catalyst composition of claim19 wherein the metallocene catalyst is represented by a formula:Cp_(m)MR_(n)X_(q) wherein Cp is a cyclopentadienyl ring which may besubstituted, or derivative thereof which may be substituted, M is aGroup 4, 5, or 6 transition metal, R is a hydrocarbyl group orhydrocarboxy group having from one to 20 carbon atoms, X may be ahalide, a hydride, an alkyl group, an alkenyl group or an arylalkylgroup, and m=1-3, n=0-3, q=0-3, and the sum of m+n+q is equal to theoxidation state of the transition metal.
 22. The metallocene supportedcatalyst composition of claim 19 wherein the fluorine concentration isin the range of from 0.6 to 3.5 wt. % of support.